DE19605243A1 - Process for the production of pure lead oxide from used batteries - Google Patents
Process for the production of pure lead oxide from used batteriesInfo
- Publication number
- DE19605243A1 DE19605243A1 DE1996105243 DE19605243A DE19605243A1 DE 19605243 A1 DE19605243 A1 DE 19605243A1 DE 1996105243 DE1996105243 DE 1996105243 DE 19605243 A DE19605243 A DE 19605243A DE 19605243 A1 DE19605243 A1 DE 19605243A1
- Authority
- DE
- Germany
- Prior art keywords
- solution
- ketone
- lead oxide
- paste
- lead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 19
- 229910000464 lead oxide Inorganic materials 0.000 title claims description 16
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- -1 dimethyl ketone ketone Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910006529 α-PbO Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/06—Lead monoxide [PbO]
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Description
Die Erfindung bezieht sich auf ein verbessertes Verfahren zur Wiedergewinnung von Blei aus verbrauchten Batterien. Insbe sondere bezieht sich die Erfindung auf ein verbessertes Verfahren zur Wiedergewinnung von Blei als reines Bleioxid aus verbrauchter Paste, die aus verbrauchten Säurebatterien erhalten wird, welches auch Umwelt- und Verschmutzungsproble me löst.The invention relates to an improved method for Recovery of lead from used batteries. In particular special, the invention relates to an improved Process for the recovery of lead as pure lead oxide from used paste, from used acid batteries is obtained, which also environmental and pollution problems me solves.
Die Wiedergewinnung des Bleis aus verbrauchten Säurebatterien wurde in den letzten 60 Jahren ausführlich erforscht und wird in großem Maßstab durchgeführt. Das akute Problem der Ver schmutzung trug zu einem erhöhten Interesse in den letzten Jahren auf der Suche nach neuen Verfahren bei, welche weniger Verschmutzungs- und Umweltprobleme als die bekannten pyro metallurgischen Verfahren hervorrufen.The recovery of the lead from spent acid batteries has been and will be extensively researched over the past 60 years carried out on a large scale. The acute problem of ver Soiling has contributed to increased interest in the past Years looking for new processes which less Pollution and environmental problems than the well-known pyro cause metallurgical processes.
Schon 1915 wurde in der US-Patentschrift Nr. 1 148 062 ein Verfahren zur Wiedergewinnung von Blei aus verbrauchten Batterien beschrieben. Nach diesem Patent wird extrahierte verbrauchte Batteriepaste oder -masse in Bleioxide durch Kalzinieren und Entschwefeln umgewandelt, aber die erzeugten Oxide sind nicht von hoher Reinheit.Already in 1915, US Pat. No. 1,148,062 was used Process for the recovery of lead from spent Batteries described. After this patent is extracted used battery paste or mass in lead oxide Calcined and desulfurized, but converted Oxides are not of high purity.
Gemäß der US-Patentschrift Nr. 4 222 769 wird eine extrahier te verbrauchte Batteriepaste entschwefelt und sodann in metallisches Blei durch Rösten in Anwesenheit eines Kohlen stoffreduktionsmittels umgewandelt.According to U.S. Patent No. 4,222,769, an extract is disclosed desulphurized battery paste and then in metallic lead by roasting in the presence of a carbon substance reducing agent converted.
In der US-Patentschrift Nr. 4 769 116 wird eine Paste aus verbrauchten Säurebatterien erhalten und mit Natriumhydroxid behandelt, wodurch eine Lösung von Natriumsulfat und eine entschwefelte Paste hergestellt wird. Das reine metallische Blei wird sodann aus der entschwefelten Paste durch elektro lytische Extraktion wiedergewonnen.In U.S. Patent No. 4,769,116 a paste is made conserved spent acid batteries and with sodium hydroxide treated, creating a solution of sodium sulfate and a desulfurized paste is produced. The pure metallic Lead is then made from the desulfurized paste by electro lytic extraction recovered.
Gemäß der Deutschen Patentschrift Nr. 3 637 270 wird der Bleibestandteil aus verbrauchten Batterien durch Extraktion mit einer wäßrigen Lösung einer Mineralsäure wiedergewonnen, worauf mit einer Lösung von Wasserstoffperoxid behandelt wird und Pb⁺⁺-Ionen erhalten werden. Ein diesem Verfahren zuzuschreibender besonderer Vorteil ist die hohe Wiedergewin nung von Blei und die Verwendung von ungiftigen Reaktionsmit teln.According to German Patent No. 3 637 270, the Lead component from used batteries by extraction recovered with an aqueous solution of a mineral acid, followed by treatment with a solution of hydrogen peroxide and Pb⁺⁺ ions can be obtained. This procedure The particular advantage is the high recovery lead and the use of non-toxic reaction agents teln.
In einer verhältnismäßig neuen US-Patentschrift (5 211 818) wird der Schlamm der aus den verbrauchten Batterien erhalte nen Paste mit einer Lösung von Ammoniumsulfat behandelt, und der metallische Bleibestandteil wird durch elektrolytische Extraktion wiedergewonnen.In a relatively new U.S. patent (5,211,818) will get the sludge from the used batteries NEN paste treated with a solution of ammonium sulfate, and the metallic lead component is replaced by electrolytic Extraction recovered.
Wie aus der obigen kurzen Darstellung entnommen werden kann, liegt in den meisten älteren Druckschriften das aus verbrauch ten Battieren wiedergewonnene Blei in seiner metallischen Form vor, das entsprechend den jeweiligen Marktanforderungen in die entsprechenden Oxide umgewandelt werden muß.As can be seen from the brief description above, this is due to consumption in most older publications ten Battieren recovered lead in its metallic Form before that according to the respective market requirements must be converted into the corresponding oxides.
Aufgabe der Erfindung ist die Schaffung eines verbesserten Verfahrens zur Wiedergewinnung des Bleibestandteils aus einer Paste, die von verbrauchten Batterien gewonnen wird. Dabei soll reines Bleioxid aus einer Paste erzeugt werden, die aus verbrauchten Batterien gewonnen wird, ohne daß gefährliche Stoffe und verunreinigende Gase erzeugt werden. Das Verfahren soll wirtschaftlich sein und reines Bleioxid aus einer Paste gewinnen, die aus verbrauchten Batterien erhalten wird.The object of the invention is to provide an improved Process for the recovery of the lead component from a Paste obtained from used batteries. Here pure lead oxide is to be generated from a paste that is made from used batteries is recovered without dangerous Substances and contaminating gases are generated. The procedure should be economical and pure lead oxide from a paste win, which is obtained from used batteries.
Diese Aufgabe wird erfindungsgemäß durch die Merkmale des Anspruchs 1 gelöst.This object is achieved by the features of Claim 1 solved.
Die Unteransprüche sind auf vorteilhafte Ausgestaltungen der Erfindung gerichtet.The subclaims relate to advantageous embodiments of the Invention directed.
Die Erfindung wird nachfolgend in Verbindung mit dem Fließ schema gemäß Fig. 1 näher erläutert.The invention is explained in connection with the flow scheme according to FIG. 1 in more detail.
Im ersten Schritt wird die vorher kalzinierte und entschwe felte verbrauchte Paste mit einer konzentrierten Lösung von Natriumhydroxid oder Kaliumhydroxid, vorzugsweise in einer Konzentration zwischen 40 Gew.-% und 70 Gew.-% kontaktiert, die wahlweise zwischen 30 und 45 g Natrium- oder Kaliumsulfat je Liter der Lösung enthält. Die Aufschlämmung wird gefil tert, und man erhält so ein klares Filtrat, welches das Bleioxid enthält. Es hat sich gezeigt, daß die Anwesenheit einer kleinen Menge Sulfat, wie Natriumsulfat oder Kaliumsul fat, eine vorteilhafte Wirkung auf die Reinheit des Bleioxid produkts hat.In the first step, the previously calcined and removed felt used paste with a concentrated solution of Sodium hydroxide or potassium hydroxide, preferably in one Concentration contacted between 40% by weight and 70% by weight, the choice between 30 and 45 g of sodium or potassium sulfate contains per liter of solution. The slurry is filmed tert, and you get a clear filtrate, which the Contains lead oxide. It has been shown that the presence a small amount of sulfate such as sodium sulfate or potassium sulfate fat, a beneficial effect on the purity of the lead oxide product.
Im zweiten Schritt wird ein flüchtiges Keton zu dem erhalte nen Filtrat beigegeben, welches eine schnelle Verdampfungs kühlung des im ersten Schritt erhaltenen Filtrats bewirkt, wobei eine Temperatur im Bereich zwischen 50 C und 75°C erreicht und so eine Suspension des Bleioxids erzeugt wird. Obwohl das Verhältnis zwischen dem Keton und der das Bleioxid enthaltenden Alkalilösung nicht so kritisch ist, liegt das bevorzugte Gewichtsverhältnis zwischen 0,1 und 0,6 und ist gemäß der Temperatur des Filtrats, der Art des Ketons sowie dem Ausmaß des Rührens zu wählen. Schließlich wird im letzten Schritt die Suspension gefiltert und das niedergeschlagene Bleioxid wird mit Wasser gewaschen, wodurch man ein reines α-Bleioxid erhält, das weniger als 0,004% Verunreinigungen enthält, welche allgemein aus Antimon, Eisen, Barium und Kupfer bestehen. Die zwei getrennten flüssigen Phasen, d. h. Alkalilösung und das jeweilige Keton, werden in das Verfahren rezykliert.In the second step, a volatile ketone is obtained NEN filtrate added, which is a quick evaporation cooling the filtrate obtained in the first step, with a temperature in the range between 50 C and 75 ° C reached and a suspension of the lead oxide is generated. Although the ratio between the ketone and the lead oxide containing alkali solution is not so critical, that is preferred weight ratio is between 0.1 and 0.6 according to the temperature of the filtrate, the type of ketone and choose the extent of stirring. Finally, in the last Step filtered the suspension and the precipitated Lead oxide is washed with water, making one pure α-lead oxide receives less than 0.004% impurities contains, which generally consists of antimony, iron, barium and Copper exist. The two separate liquid phases, i.e. H. Alkali solution and the respective ketone are used in the process recycled.
Ein besonders vorteilhaftes Merkmal des Verfahrens ist die kurze Zeitspanne, die erforderlich ist, wobei der ganze Zyklus nur etwa 45 bis 60 Minuten dauert.A particularly advantageous feature of the method is short period of time that is required, taking the whole Cycle lasts only about 45 to 60 minutes.
Die Erfindung wird nachfolgend durch die folgenden Beispiele erläutert, wobei zu bemerken ist, daß diese Beispiele nur zu einem besseren Verständnis der Erfindung dienen, ohne irgend eine Einschränkung zu bedeuten, wobei das Verfahren durch die beigefügten Patentansprüche bestimmt wird.The invention is illustrated below by the following examples explained, it should be noted that these examples only go to serve a better understanding of the invention without any to mean a limitation, the method by attached claims is determined.
In den Beispielen sind die Konzentrationen in Gewichtsprozent angegeben, wenn nichts anderes gesagt wird. In the examples, the concentrations are in percent by weight unless otherwise stated.
Eine Menge von 179,5 g Paste, die aus verbrauchten Säurebat terien gewonnen war, wurde nach dem Kalzinieren und Entschwe feln durch 1000 cm³ einer Lösung ausgelaugt, die 964 g Natriumhydroxid und 36 g Natriumsulfat enthielt und auf etwa 130°C erhitzt wurde.An amount of 179.5 g of paste made from spent acid bath terie was obtained after calcining and decongesting leached through 1000 cm³ of a solution, the 964 g Contained sodium hydroxide and 36 g of sodium sulfate and about Was heated to 130 ° C.
Die heiße alkalische Lösung wurde nach Abtrennen von der erhaltenen Aufschlämmung in ein Gefäß eingegeben, das mit einem Wiederverflüssigungskondensator und einem Mischer versehen war und in das Aceton in einem Verhältnis von Aceton zu Alkalibleilösung von 0,25 bezogen auf das Gewicht zugege ben wurde. Das verflüchtigte Azeton, das sich im Kondensator kondensierte, wurde zum Gefäß zurückgeleitet, während die Endtemperatur in demselben auf etwa 57°C abfiel.The hot alkaline solution was removed from the the resulting slurry is placed in a vessel containing a re-liquefaction condenser and a mixer was provided and in the acetone in a ratio of acetone to alkali metal solution of 0.25 by weight ben was. The volatilized acetone that is in the condenser condensed was returned to the vessel while the Final temperature in the same dropped to about 57 ° C.
In der erhaltenen Masse wurden 176 g eines niedergeschlagenen α-Bleioxids in seiner tetragonalen Form aus einem Liter der Alkalilösung gefunden. Das niedergeschlagene Bleioxid wurde ausgefiltert, mit Leitungswasser gewaschen und es zeigte sich, daß es nur eine geringe Menge von Verunreinigungen enthielt, hauptsächlich Antimon, Barium, Eisen und Kupfer. Das verwendete Aceton und die Alkalilösung, als getrennte Phasen vorhanden, wurden getrennt und in die jeweiligen Stufen des Verfahrens rezykliert.In the mass obtained, 176 g of a precipitated one α-lead oxide in its tetragonal form from one liter of Alkali solution found. The downed lead oxide was filtered out, washed with tap water and it showed themselves that there is only a small amount of impurities contained mainly antimony, barium, iron and copper. The acetone and the alkali solution used as separate Phases existed, were separated and into the respective Stages of the process recycled.
Der Versuch von Beispiel 1 wurde unter Verwendung der glei chen Paste und der gleichen Konzentration des Natrium hydroxids wiederholt, jedoch betrug die Temperatur während des Auslaugens nur 110°C. Eine Menge von 88 g der Paste wurde durch 1000 cm³ der Alkalilösung ausgelaugt, welche ferner 29 g Natriumsulfat enthielt.The experiment of Example 1 was carried out using the same Chen paste and the same concentration of sodium hydroxide repeated, but the temperature was during leaching only 110 ° C. An amount of 88 g of the paste was added leached by 1000 cm³ of the alkali solution, which further Contained 29 g of sodium sulfate.
Die erhaltene Lösung wurde mit Aceton kontaktiert, wobei das Verhältnis Aceton : Alkali 0,25, bezogen auf das Gewicht, betrug. Das niedergeschlagene Produkt bestand aus 85,6 g α-PbO von sehr hoher Reinheit mit nur 0,004% fremden Katio nen, hauptsächlich Eisen, Antimon, Barium und Kupfer.The solution obtained was contacted with acetone, the Ratio acetone: alkali 0.25, based on the weight, scam. The precipitated product consisted of 85.6 g Very high purity α-PbO with only 0.004% foreign catio mainly iron, antimony, barium and copper.
Claims (6)
- (a) Auslaugen der kalzinierten und entschwefelten verbrauchten Paste durch eine wäßrige konzentrierte Lösung, die ein Alkalihydroxid enthält, bei einer Tempe ratur von über 100°C, und Abtrennen der Lösung vom Rest;
- (b) Niederschlagen des Bleioxids aus der im Schritt (a) erhaltenen Lösung durch Zugeben eines flüchtigen Ketons und
- (c) Abtrennen des Bleibestandteils aus der erhalte nen Suspension und dadurch nach dem Waschen Erzeugen eines reinen α-Bleioxids, wobei die Alkalilösung und das Keton in das Verfahren rezykliert werden.
- (a) leaching the calcined and desulphurized spent paste through an aqueous concentrated solution containing an alkali hydroxide at a temperature of over 100 ° C, and separating the solution from the rest;
- (b) depositing the lead oxide from the solution obtained in step (a) by adding a volatile ketone and
- (c) separating the lead constituent from the suspension obtained and thereby producing a pure α-lead oxide after washing, the alkali solution and the ketone being recycled into the process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL11675396A IL116753A0 (en) | 1996-01-14 | 1996-01-14 | A process for the manufacture of pure lead oxide from exhausted batteries |
| PCT/IL1997/000213 WO1998058878A1 (en) | 1996-01-14 | 1997-06-25 | Process for the manufacture of lead oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19605243A1 true DE19605243A1 (en) | 1997-07-17 |
Family
ID=26322210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1996105243 Withdrawn DE19605243A1 (en) | 1996-01-14 | 1996-02-13 | Process for the production of pure lead oxide from used batteries |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5840262A (en) |
| AU (1) | AU3188597A (en) |
| DE (1) | DE19605243A1 (en) |
| GB (1) | GB2309030A (en) |
| IL (1) | IL116753A0 (en) |
| WO (1) | WO1998058878A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7507496B1 (en) * | 2004-12-07 | 2009-03-24 | Toxco, Inc | Process for recovering lead oxides from exhausted batteries |
| ITBR20050002A1 (en) | 2005-04-19 | 2006-10-20 | Stc S R L Software | PROCEDURE FOR THE PRODUCTION OF HYDRATE OR LEAD OXIDE WITH PURITY HIGH OF MATERIALS AND / OR RESIDUES CONTAINING LEAD IN THE FORM OF SULFATES AND EVENTUALLY OF OXIDES AND / OR OTHER COMPOUNDS. |
| ITVA20070007A1 (en) | 2007-01-17 | 2008-07-18 | Millbrook Lead Recycling Techn | RECOVERY OF THE LEAD OF HIGH-PURITY CARBONATE UNIFORM PASTEL RECOVERY FROM THE CRUSHING OF EXHAUSTED LEAD ACCUMULATORS |
| ITMI20072257A1 (en) * | 2007-11-30 | 2009-06-01 | Engitec Technologies S P A | PROCESS FOR PRODUCING METALLIC LEAD FROM DESOLFORATED PASTEL |
| ITBR20100001A1 (en) * | 2010-03-29 | 2011-09-30 | Stc S R L Science Technology & C Onsulting | PROCEDURE FOR RECOVERY AND SELECTIVE RECYCLING OF COMPONENTS CONSTITUTING LEAD-TO-LEAD BATTERIES. |
| CN103022593B (en) * | 2011-09-26 | 2015-04-29 | 深圳市雄韬电源科技股份有限公司 | Method for preparing lead tetraoxide from waste lead-acid batteries and application |
| US9670565B2 (en) | 2014-06-20 | 2017-06-06 | Johnson Controls Technology Company | Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries |
| US9555386B2 (en) | 2014-06-20 | 2017-01-31 | Johnson Controls Technology Company | Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries |
| CN104141045B (en) | 2014-08-20 | 2017-04-12 | 北京化工大学 | Method for recovering lead oxide from waste lead plaster |
| CN104393364B (en) * | 2014-11-13 | 2017-07-14 | 张家港智电芳华蓄电研究所有限公司 | A kind of method for preparing PbO from the direct wet method of waste lead acid battery |
| US10062933B2 (en) | 2015-12-14 | 2018-08-28 | Johnson Controls Technology Company | Hydrometallurgical electrowinning of lead from spent lead-acid batteries |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1148062A (en) * | 1908-05-22 | 1915-07-27 | Clarence E Tucker | Method of utilizing battery-waste. |
| US1915724A (en) * | 1930-05-12 | 1933-06-27 | Finkelstein Alexis | Manufacture of lead oxide |
| JPS5493626A (en) * | 1978-01-06 | 1979-07-24 | Diamond Eng Co Ltd | Method of regenerating and recovering lead from leaddsulfateecontaining waste product |
| US4220628A (en) * | 1978-10-10 | 1980-09-02 | N L Industries, Inc. | Production of lead monoxide from lead sulfate with acidic ammonium acetate |
| US4269810A (en) * | 1978-10-10 | 1981-05-26 | Nl Industries, Inc. | Method for desulfation of battery mud |
| IT1139420B (en) * | 1981-09-02 | 1986-09-24 | Umberto Ducati | HYDRO-METALLURGICAL PROCEDURE FOR THE RECOVERY OF METALLIFERAL MATERIALS FROM EXHAUSTED LEAD ACID ACCUMULATORS |
| IT1188203B (en) * | 1985-11-19 | 1988-01-07 | Tecneco Spa | HYDROMETALLURGIC PROCESS TO RECOVER IN LEAD METALLIC FORM THE LEAD CONTAINED IN THE ACTIVE MASS OF THE EXHAUSTED BATTERIES |
| IT1191650B (en) * | 1986-01-09 | 1988-03-23 | Tecneco Spa | HYDROMETALLURGIC PROCESS FOR A TOTAL RECOVERY OF THE COMPONENTS OF EXHAUSTED LEAD ACID BATTERIES |
| DE3612491A1 (en) * | 1986-04-14 | 1987-10-15 | Preussag Ag Metall | Process for recovering lead from oxidic or oxidic/sulphatic secondary precursor materials |
| US5173277A (en) * | 1991-02-22 | 1992-12-22 | Nl Industries, Inc. | Methods for processing battery waste and other lead-contaminated materials |
| US5211818A (en) * | 1991-04-09 | 1993-05-18 | Moure Jr William B | Method for recovering lead from batteries |
| RU2016104C1 (en) * | 1992-05-27 | 1994-07-15 | Ходов Николай Владимирович | Method of storage battery lead bearing scrap processing |
-
1996
- 1996-01-14 IL IL11675396A patent/IL116753A0/en unknown
- 1996-02-07 US US08/597,821 patent/US5840262A/en not_active Expired - Fee Related
- 1996-02-07 GB GB9602464A patent/GB2309030A/en not_active Withdrawn
- 1996-02-13 DE DE1996105243 patent/DE19605243A1/en not_active Withdrawn
-
1997
- 1997-06-25 AU AU31885/97A patent/AU3188597A/en not_active Abandoned
- 1997-06-25 WO PCT/IL1997/000213 patent/WO1998058878A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| GB9602464D0 (en) | 1996-04-03 |
| US5840262A (en) | 1998-11-24 |
| IL116753A0 (en) | 1996-05-14 |
| GB2309030A (en) | 1997-07-16 |
| WO1998058878A1 (en) | 1998-12-30 |
| AU3188597A (en) | 1999-01-04 |
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